Acetic Acid → Tert-butyl 3-(diethylamino)benzylcarbamate

HRID 2071003Notes

Reaction equation

HRID 2071003 reaction equation
[CH:1](=O)[CH3:2].[NH2:4][C:5]1[CH:6]=[C:7]([CH:17]=[CH:18][CH:19]=1)[CH2:8][NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13].[BH3-]C#N.[Na+].[CH3:24][C:25](O)=O>CC#N.O>[CH2:24]([N:4]([CH2:1][CH3:2])[C:5]1[CH:6]=[C:7]([CH:17]=[CH:18][CH:19]=1)[CH2:8][NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH3:25]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 177AcetaldehydeHCID 5003444Sodium cyanoborohydrideHCID 10775412tert-butyl N-((3-aminophenyl)methyl)carbamate

Product 1

HCID 68671365Tert-butyl 3-(diethylamino)benzylcarbamateYield 77%

Reagents, catalysts & solvents 1

HCID 18373917Acetonitrile--water (1/1)Solvent

Conditions

Temperature
0 °C

Procedure

Acetaldehyde (0.52 ml, 0.4 g, 9.08 mmol, 5 eq) was added to a stirred solution of tert-butyl 3-aminobenzylcarbamate (derived from 3-(aminomethyl)aniline (TCI America)) in 11 ml CH3CN/H2O (10:1) at 0° C. After 5 min NaBH3CN (0.3 g, 4.54 mmol, 2.5 eq) was added. The reaction was adjusted to pH {tilde over ( )} 7 with HOAc and stirred at 0° C. for 5 min. The ice-bath was removed and the reaction was stirred at room temperature for 45 min. The solvent was removed in vacuo. The residue was diluted with saturated aqueous NaHCO3 and extracted with EtOAc (×2). The combined organics were washed with water (×3), brine (×1), and dried over Na2SO4. The inorganics were filtered off, and the solvent was removed in vacuo. Purification via flash chromatography yielded 0.3875 g (1.4 mmol, 77% yield) of tert-butyl 3-(diethylamino)benzylcarbamate.

Workup

  1. customThe ice-bath was removed
  2. stirringthe reaction was stirred at room temperature for 45 min
  3. customThe solvent was removed in vacuo
  4. additionThe residue was diluted with saturated aqueous NaHCO3
  5. extractionextracted with EtOAc (×2)
  6. washThe combined organics were washed with water (×3), brine (×1)
  7. dry with materialdried over Na2SO4
  8. filtrationThe inorganics were filtered off
  9. customthe solvent was removed in vacuo
  10. customPurification via flash chromatography

Sources & evidence

ORD record
ord-6923e1b0b96f4fe4a12f762793e92e89
Source dataset
uspto-grants-2012_10
Patent number
US08299267B2

Reaction notes

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